Clay Mineral XRD Sample Preparation

and Interpretation
Ceramic XRD patterns

Connie Constan, guest lecture

EPS 400, 04/04/2012
 What are clays?
• Fine-grained
• Earthy
• Plastic when moist

• Group of minerals
• Category of rocks and soils
• Particle-size grade (<2µm)
 Phyllosilicates
• kaolin group (two-layer clays)
• smectite group (three-layer, expanding lattice)
• illite group (three-layer, non-expanding)
• chlorite group (three-layer with interlayer cations)

Images from Railsback's

Some Fundamentals of
Mineralogy and
Geochemistry
 Hydrous-Magnesian Clays
• Lath structure clays
• Chain-like arrangement

• palygorskite group
• sepiolite group
Sepiolite/Meerschaum pipe bowls
 Sample Preparation

• Constraints
– Supplies and equipment
available
USGS Open-File Report 01-041
– Purpose of analysis
– Material itself
– Your knowledge and
ingenuity

USGS Open-File Report 01-041

 Disaggregate the Rock

Mortar and Pestle Utrasonic Probe

Waring Laboratory Blender McCrone Micronising Mill

 Chemical Pretreatments
• Removal of carbonates
These acids can cause burns. Wear
– Acetic acid goggles, plastic gloves, and an apron
while working with these chemicals.
• Removal of organics
– Hydrogen peroxide

• Removal of sulfates
• Removal of iron oxides

USGS Open-File Report 01-041

• Cation saturation
 Particle Size Separation
• Methods
– Decantation
– Centrifugation

• Settling times USGS Open-File Report 01-041

– Stoke’s Law

• Dispersant/deflocculant
– sodium
hexametaphosphate USGS Open-File Report 01-041
 Oriented Methods
• Why?

USGS Open-File Report 01-041

Velde and Druc 1999: Figure 3.8

 Glass Slide
• Advantage
– Quick
• Disadvantage Moore and Reynolds Figure 6.1

– All
• Level of skill needed
– Low
• Application
– Qualitative analysis
USGS Open-File Report 01-041
 Smear Mount
• Advantage
– Quick, moderately
homogenous
• Disadvantage
– Most USGS Open-File Report 01-041

• Level of skill needed

– Moderate
• Application
– Clay and nonclay
minerals USGS Open-File Report 01-041
 Filter Transfer
• Advantage
– Homogenous aggregate
• Disadvantage
– Fair intensities
• Level of skill needed
– Moderate
• Application
– Quantitative
representation

Images from USGS Open-File Report 01-041

 Porous Plate
• Advantage
– Best intensities
• Disadvantage
– Inhomogeneous
aggregate Moore and Reynolds Figure 6.4

• Level of skill needed

– High
• Application
– Crystal structure studies

Porous Ceramics
www.sentrotech.com
Ethylene Glycol Solvation

Images from USGS Open-File Report 01-041

 Random Mount

• Why?

USGS Open-File Report 01-041

Moore and Reynolds Figure 6.5
 New Instrumentation!
• Rigaku SmartLab • Rigaku Rapid II
– Nanomaterials – Mounted samples
– Thin films – Thin films
– Powder & bulk – Capillaries
– Metals & alloys – 2D detector/image plate
 Microdiffraction
• Point Focus geometry in SmartLab system

CBO
CBO-f
Parabolic
Polycap

• Automated diffraction mapping in Rapid II system

General Principles of Identification
• Basal (00l) spacing

Illite Diffractogram Calculated X-ray diffraction pattern of antigorite

www.gly.uga.edu/schroeder/geol6550/CM11.htm www.gly.uga.edu/Schroeder/geol6550/CM07.html
 Illite and Glauconite

Glauconite-rich sandstone

Moore and Reynolds Figure 7.3

 Chlorite and Kaolinite

USGS Open-File Report 01-041

Moore and Reynolds Figure 7.4

 Smectite

USGS Open-File Report 01-041

Moore and Reynolds Figure 7.8

 Vermiculite

USGS Open-File Report 01-041

Moore and Reynolds Figure 7.7

Sepiolite, Palygorskite, Halloysite

• Sepiolite
6.9 deg 2θ

• Palygorskite
8.5 deg 2θ

• Halloysite
~20 deg 2θ

Scanning electron image of halloysite

www.gly.uga.edu/Schroeder/geol6550/halloysite.gif
Polytypes
• 1M and 2M1 most
common polytypes
– Use diagnostic hkl
reflections tables in
Moore and Reynolds
(Tables 7.5 to 7.7)

• Turbostratic Stacking
– Wide band at hk (13,20)
asymmetiric towards
wide angles in XRD

Figures from Meunier (2005: Figure 1.12)

 Mixed-Layered Clays
• Illite/Smectite (I/S)
– Ethylene glycol solvation
– Reichweite ordering between
5 and 8.5 degrees 2θ
– Percent illite estimation from
value of Δ2θ
• Chlorite/Smectite (C/S)
– Expansion with ethylene glycol
solvation
– Expansion with Mg saturation
and glycerol solvation
 Mixed-Layered Clays
• Chlorite/Vermiculite
– Ethylene glycol solvation
– Mg saturation
– Glycerol solvation
– Heat treatment
– Air-dried condition
– Percent from Δ2θ
• Kaolinite/Smectite
– Ethylene glycol solvation
– Heat treatment
– Percent from Δ2θ
• Serpentine/Chlorite
– Broadening of odd-
numbered peaks
– Equation to determine
percent serpentine
• Mica/Vermiculite
– Heat treatment
– Mg saturation
– Glycerol solvation
– Use low-angle reflection
(001/001) for percent
and Reichweite ordering
 Non-Clay Minerals
MINERAL TYPE SHOWN D SPACING ANGLE 2θ

Silicas α quartz 4.27, 3.342 20.8, 26.67

Feldspars K-spar, Plag 3.19, 3.24 27.95, 27.52

Zeolites solid solution series Approx. 8-9 <12

Carbonates Calcite, Dolomite 3.04, 2.89 29.43, 30.98

Sulfates Gypsum, Anhydrite 7.61, 3.50 11.7, 25.46

 Quantitative Analysis
• Required Sample Characteristics
– Length
– Thickness
– Position
– Homogeneity

Figures from Moore and Reynolds (1997)

 Quantitative Analysis
• Mineral Reference Intensities
• Peak Intensity Measurement
Smectite-rich I/S
• Peak Decomposition Well-crystallized illite (WCI)
Poorly-crystallized illite (PCI)

y
Two methods
Illite-rich I/S

FWHM Índice de Ku bler 4 6 8

°2θ, CuKα
Gharrabi et al., 1998 CCM, 46:79-88
Peak Decomposition
Righi and Elsass, 1996 CCM, 44:791-800

FWHM
8 9 10
°2Θ
Índice de Eberl y Velde
FWHM = full width at
half maximum
 Clay Quantification
• The best diffraction peaks to use are as close
together as possible
• Avoid the low diffraction angle region
• Do not use external standards
• Need random orientation when both clay and
non-clay minerals are present in a single
sample
• Use integrated intensities and calculated
calibration factors
 Clay Quantification

QUANTITATIVE X-RAY DIFFRACTION ANALYSIS OF CLAY-BEARING

ROCKS FROM RANDOM PREPARATIONS
Srodon et al 2001 Clays and Clay Minerals 49(6):514–528
 My Research
• What clay minerals were
available locally?

• What clay minerals were

used in Gallina ceramics?

Natural Clays
Geology = seven formations

Ceramics
Archaeology = three types
 My Results

Gallina Black-on-gray
ceramic sherd

Ceramic Qal Fm.

Estimated Original Firing Temperature

Clay pattern at each temperature: unfired, 300,

600, 750, and 900ºC
 Summary
• “Identifying clay minerals for their diffraction
tracing is something of a Gestalt process, i.e.,
identifying the whole – being able to say that
it is an illite/smectite because it has an
illite/smectite pattern.”
(Moore and Reynolds 1997:296)

• In other words, you just have to learn what

the characteristic patterns look like for each
clay mineral and the mixed-layered clays.